Tetra-alkyl p-phenylene diamine with aromatic primary amino color developing agent

ABSTRACT

WHEREIN EACH OF R1, R2 and R3 is C1-C6 alkyl or R1 together with R2 represent the atoms necessary to close a pyrrolidine ring, and R4 is C1-C6 alkyl or ethylene or propylene linked to the C-atom of the phenylene ring in ortho position to the amino group carrying the R4-substituent, ONE OF R1-R4 being a C2-C6 alkyl group carrying a solubilizing group. The tetraalkyl p-phenylene diamine compound increases the activity of the colour developing agent without effecting to a noteworthy extent the fog and gradation of the silver halide material. A photographic colour developing composition for silver halide material is described which comprises besides the aromatic primary amino colour developing agent a tetraalkyl p-phenylene diamine compound of the formula :

United States Patent 11 1 Ghys et al.

[4 1 Oct. 23, 1973 TETRA-ALKYL P-PHENYLENE DIAMINE WITH AROMATIC PRIMARY AMINO COLOR DEVELOPING AGENT I [75] inventors: Theofiel Hubert Ghys, Kontich;

Jozef Frans Willems, Wilrijk; George Frans Van Veelen, Mortsel,

21 Appl. No.2 178,811

[30] Foreign Application Priority Data Dec. 1, 1970 Great Britain 57,062/70 [52] US. Cl 96/55, 96/66, 96/66.3 [51] Int. Cl G03c 7/00 [58] Field of Search 96/66 R, 66.3, 55

[56] References Cited UNITED STATES PATENTS 3,265,502 8/1966 Willems et al. 96/66 R 3,615,525 l0/l97l Willems 96/66 R FOREIGN PATENTS OR APPLICATIONS 1,149,794 4/1969 Great Britain 96/66 R Primary Examiner-Norman G. Torchin Assistant ExaminerR. L. Schilling Attorney-Alfred W. Breiner [57] ABSTRACT A photographic colour developing composition for silver halide material is described which comprises besides the aromatic primary amino colour developing agent a tetraalkyl p-phenylene diamine compound of the formula I Rf wherein each of R R and R is C,C alkyl or R together with R represent the atoms necessary to close a pyrrolidine ring, and

R is C C alkyl or ethylene or propylene linked to the C-atom of the phenylene ring in ortho position to the amino group carrying the R -substituent,

one of R,-R being a C C alkyl group carrying a solubilizing group. The tetraalkyl p-phenylene diamine compound increases the activity of the colour developing agent without effecting to a noteworthy extent the fog and gradation of the silver halide material. I

6 Claims, No Drawings TETRA-ALKYL P-PHENYLENE DIAMINE WITH AROMATIC PRIMARY AMINO COLOR DEVELOPING AGENT The. present invention relates to a process for the colour development of photographic silver halide materials containing exposed silver halide and to developing compositions used therein.

It is known that the developing activity of a developing solution containing a mixture of several developing substances'can be higher than the sum of the develop ing activities of the separate developing solutions of each of these developing substances used in the same concentration as in the solution of that mixture. This phenomenon is called superadditive development.

The most common superadditive developing combinations for the development of exposed black-andwhite photographic silver halide elements are pmonomethylaminophenol together with hydroquinone and l-phenyl-3-pyrazolidinone together with hydroquinone. It is further known that certain p-phenylene diamine derivatives have a superadditive development effect when used together with hydroquinone.

It is known that for the production ofa photographic colour image in a light-sensitive silver halide layer; the exposed silver halide is developed to a silver image by means of an aromatic primary amino developing agent in the presence of a colour coupler which reacts with the oxidized developing agent to form a dyestuff on the areas corresponding to the silver image. In J.Phot.Sci.

ll (1963) 136-139, it has been shown that l-phenyl-3- pyrazolidinone and p-monomethylaminophenol also increase the activity of these aromatic primary amino colour developing agents, the first compound being the most active of the two. As is known from French Pat. No. 1,283,420 other p-aminophenol derivatives also activate colour-development by means of N,N-dialkylp-phenylene diamine developing agents.

' Though l-phenyl-3-pyrazolidinone has a high devel opment activating effect it shows the disadvantage of strongly increasing the fog and reducing the gradation; this also applies to the p-aminophenol compounds.

It has now been found that the activity of aromatic primary amino colour developing agents, used for the development of photographic silver halide elements in the presence of colour forming couplers can be increased without effecting the fog and gradation to a noteworthy extent by means of non colour forming tetra-alkyl-p-phenylene diamine derivatives corresponding to the following general formula wherein each of R R and R stands for C -C alkyl, or R, together with R represents the atoms necessary to close a pyrrolidine ring, and

R stands for c,-c alkyl or ethylene or propylene linked to the C-atom of the phenylene ring in orthoposition to the amino group carrying the R substituent, one of R R R and R being a C -C alkyl group carrying a solubilizing group which includes such groups droxyl.

Generally Therefore, in accordance with the present invention photographic developing compositions for developing, in the presence of a colour forming coupler, an exposed silver halide emulsion layer' of a photographic element are provided which comprise, in addition to an aromatic primary amino colour developing agent, a tetraalkyl-p-phenylene diamine derivative as represented by the above general formula.

The present invention also provides a process for the production of photographic colour images which comprises treating a photographic material having a layer containing developable silver halide with an aqueous alkaline solution in the presence of a colour forming coupler, an aromatic primary amino colour developing agent and a tetraalkyl-p-phenylene diamine derivative corresponding to the above general formula.

The ratio of tetraalkyl-p-phenylene diamine derivative corresponding to the above general formula to aromatic primary amino colour developing agent used in accordance with the present invention, can vary within wide limits. A strong superadditive effect is obtained already with a ratio of 50 mg of tetraalkyl-p-phenylene diamine derivative to 3 g of colour developing agent.

the amount of the tetraalkyl-pphenylenediamine derivative is comprised between l0 mg and l g per litre.

Representative examplesof compounds corresponding to the above general formula are l .N ,N-diethyl-N-2-hydroxyethyl-N'-ethyl-pphenylenediamine disulphate N,N-diethyl-N'-4-sulphobutyl-N'-ethyl-pphenylenediamine hydrochloride 3. N,N-diethyl-N'-3-sulphopropyl-N-propyl-pphenylenediamine 4. N,N-diethyl-N'-3-carboxypropyl-N-ethyl-ppehnylenediamine dihydrochloride 5. l-(4-sulphobutyl)-6-diethylamino-l ,2,3 ,4-

tetrahydroquinoline v 6. l-( 2-hydroxyethyl)-6-diethylaminol ,2,3 ,4'-

' tetrahydroquinoline dihydrochloride 7. l-ethyl-6-(N-ethyl-N-3-sulphopropylamino)- 1,2,3 ,4-tetrahydroquinoline 8. l-(3-sulphopropyl)-6-(N-ethyl-N-methylamino)- 1,2,3 ,4-tetrahydroquinoline l-( 3-carboxypropyl)-6-diethylaminol ,2,3 ,4- tetrahydroquinoline l0. l-(B-methylsulphonamidoethyl)-6-diethylaminol,2,3,4-tetrahydroquinoline dihydrochloride.

l l l-(p-N-ethyl-N-sulphopropylamino-phenyl)- pyrrolidine hydrochloride.

The above compounds can be prepared as illustrated in United Kingdom Pat. Nos. 989,383 and l,l9l,535.

The tetraalkyl-p-phenylene diamine compounds of the above general formula can be used in processes wherein the colour-forming couplers are dissolved in the developer as well as in processes wherein the colour-for ming couplers are incorporated in the photographic element. They can be used in negative processes as well as in reversal processes.

The tetraalkyl-p-phenylene diamine compounds of the above general formula are effective not only when used in the colour developing solution comprising the aromatic primary amino colour developing agent but also when used in a supplemental alkaline treating solu- 3 tion included in the colour processing directly after the colour development step.

The compounds corresponding to the above general formula are used to advantage in producing colour images using any of the well known aromatic primary amino colour developing agents more particularly N,N-dialkyl-p-phenylene diamines and derivatives thereof, e.g., the toluene analogues. All of these colour developing agents have an unsubstituted amino group which enables the oxidation product of the developing agent to couple with the colour forming couplers to form a dye image. Typical examples of aromatic primary amino colour developing agents are N,N-diethyl-p-phenylene diamine, 2-amino-5-diethylaminotoluene, N-butyl-N-sulphobutyl-p-phenylene diamine, 2-amino-5-[N-ethyl-N (B-methylsulphonamido)ethyl] aminotoluene, N-ethyl-N-B- hydroxyethyl-p-phenylene diamine, etc. These developing agents are usually used in the salt form such as the hydrochloride or sulphate.

Alkali, alkali metal sulphites, alkali metal halides, thickening agents such as carboxymethyl cellulose for making viscous developers, and any of the other additives included in colour developing solutions such as hydroxylamine and derivatives such as N,N-diethylhydroxylamine may be used in the colour developers employed in the colour development process of the present invention.

In the subtractive three-colour photography usually a photographic multilayer colour element is used containing a red-sensitized, a green-sensitized and a bluesensitive silver halide emulsion layer wherein on colour development, by the use of appropriate colour couplers, a cyan, magenta and yellow dyestuff image are formed, respectively. Other multicolour elements have the three differently sensitized silver halide grains dispersed in a single emulsion layer, e.g., an emulsion layer of the mixed packet type as described in U.S. Pat. No. 2,698,794 or an emulsion layer of the mixed grain type as described in U.S. Pat. No. 2,592,243.

As stated above, the colour forming couplers may be soluble colour couplers used in the colour developer or non-diffusible colour couplers incorporated in the photographic element. Usually naphtholic or phenolic couplers are used to form the cyan dye image, indazolone or pyrazolone couplers to form the magenta dye image, and open chain ketomethylene couplers to form the yellow dye image.

The compounds corresponding to the above general formula may also be used to activate colour development, by means of aromatic primary amino colour developing agents, of radiographic colour materials, for example of the kind described in U.S. Pat. application Ser. Nos. 852,236 and 852,246. In U.S. Pat. application Ser. No. 852,236 a method is described and claimed for the production of colour radiographs according to which in a recording material comprising one or more silver halide emulsions a developable silver image is formed by means of directly or indirectly recorded penetrating radiation the said material being processed in such a way that at least two images of contrasting colour and of opposite gradation are obtained. In U.S. Pat. application Ser. No. 852,246 a method is described and claimed according to which monochromic radiographic images are produced, optionally together with a silver image, thus offering more visual retrieval of information than corresponding black-and-white radiographic images.

For the purpose of accelerating the colour development of photographic elements by means of the aro- 5 matic primary amino colour developing agent together with a tetraalkyl-p-phenylene diamine derivative of the above formula, the said elements can be developed in the presence of development accelerators. These development accelerators can be used either in a silver halide emulsion layer of the photographic element or in the developing composition itself. They include alkylene oxide compounds of various types for example alkylene oxide condensation products or polymers as described in U.S. Pat. Nos. 1,970,578; 2,240,472; 2,423,549; 2,441,389; 2,531,832 and 2,533,990 and in United Kingdom Pat. Specification Nos. 920,637; 940,051; 945,340; 991,608 and 1,015,023. Other development accelerating compounds are onium and polyonium compounds preferably of the ammonium, sulphonium and phosphonium type, including onium polyoxyalkylene salts especially polyoxyalkylene bispyridinium salts examples of which can be found in U.S. Pat. No. 2,944,900, etc.

The following examples illustrate the present invention.

EXAMPLE 1 An exposed multilayer colour photographic negative film carrying three differently sensitized emulsion layers containing cyan, magenta, and yellow colour formers respectively was developed for 6 min. at 24C in a colour developer, made up according to the following recipe water 900 ml sodium hexametaphosphate 1 g sodium sulphite (anh.) 4 g N,N-diethyl-p-phenylene diamine hydrochloride 2.7 g sodium carbonate (anh.) 25 g sodium hydroxide 0.5 g potassium bromide 2.2 g hydroxylamine hydrochloride 1.2 g water to make 1000 ml (pH 10.7) On completion of the development step the photo- 5 graphic material was rinsed and transferred for 2 min. to an acid hardening fixer of the following composition water 800 ml sodium thiosulphate (anh.) 200 g sodium bisulphite 12 g glacial acetic acid 12 m1 borax 20 g potassium alum 15 g water to make 1,000 ml (pH 3.9)

The photographic material was then washed and transferred for 3 min. to a silver bleach bath of the following composition water 800 ml potassium bromide 15 g potassium ferricyanide 75 g potassium aluminium sulphate 15 g sodium acetate 5 g acetic acid 10 g water to make 1000 ml (pl-I 3.65)

After having rinsed the material it was treated again for 2 min. in the above fixing solution whereupon it was finally washed and dried.

The sensitometric results obtained are listed in the following table as compared with the results obtained when one of the compounds listed in the table below are added to the colour developer in an amount of 0.2

compound corresponding to the general fordiamine mula:

millimole per litre. 5

TABLE Blue-sensitive layer Green-sensitized layer Red-sensitized layer Compound Grada- Rel. Grada- Rel. Grada- Rel. added Fog tion speed Fog tion speed Fog tion speed None 0.14 0.48 100 0.16 0.49 100 0.09 0.42 100 Compound 2.-.. 0.16 0.55 155 0.17 0.49 155 0.09 0.44 183 Compound 3.-.. 0.14 0.58 145 0.16 0.48 142 0.09 0.46 155 Compound 4 0.15 0.67 148 0.17 0.53 146 0.09 0.50 175 parison developer comprising no superadditive developing compound is given a value of 100.

The above results show that the compounds corresponding to the above general formula accelerate development and, with approximately the same fog-value, increase the speed without adversely affecting the gradation.

The same favourable results are obtained when instead of adding the tetraalkyl-p-phenylene diamine derivatives to the developing solution the material was treated after development with an alkaline solution (pH 10.7) of these compounds.

EXAMPLE 2 A radiographic colour material comprising a polyethylene terephthalate support and on both sides thereof a high-speed gelatin silver bromoiodide emulsion comprising a colour coupler, was exposed through a wedge and colour processed to yield a coloured wedge print. Development occurred by treatment of the exposed material for 27 sec. at 40C in a colour developer comprising N-ethyl-N-B-hydroxyethyl-p-phenylene diamine as colour developing agent and one of the superadditive black-and-white developing agents listed in the table below.

The sensitometric results obtained are listed in the table below. The values given for the speed are relative values measured at density 1 above fog. The value of 100 was given to the speed of the material developed in a developer comprising no superadditive developing agent. The values given for the gradation were measured behind a red filter between density 0.25 and 2.0 above the fog value.

TABLE Grada- Rela-- Compound added per litre Fog tion tive speed none O.l6 2.45 100 0.62 mmole of l-phenyl-3-pyrazolidinone 0.80 3.07 235 0.62 mmole of compound 2 0.24 2.73 135 0.62 mmole of compound 3 0.25 2.67 I35 wherein:

eachof R R and R stands for C C alkyl or R together with R represents the atoms necessary to close a pyrrolidine ring, and R stands for C C alkyl or ethylene or propylene linked to the C-atom of the phenylene ring in ortho position to the amino group carrying the R substituent,

one of Ii -R being a C -C alkyl group carrying a solubilizing group which is a member of the group consisting of carboxyl, sulpho, ionizable sulphonarnide, and hydroxyl.

- 2. A photographic developer-composition according to claim 1, wherein the aromatic primary amino colour developing agent is a N,N-dialkyl-p-phenylene diamine or toluene analog thereof.

3. A process of producing photographic colour images which comprises treating a developable silver halide emulsion layer in the presence of a colour coupler with a developer composition which comprises an aromatic primary amino colour developing agent and a tetraalkyl p-phenylene diamine compound corresponding to the general formula:

wherein: each .of R R and R stands for C C alkyl or R, together with R represents the atoms necessary to close a pyrrolidine ring, and R stands for C -C alkyl or ethylene or propylene linked to the C-atom of the phenylene ring in ortho position to the amino group carrying the R substituent, one of R -R, being a C2-C6 alkyl group carrying a solubilizing group which is a member of the group consisting of carboxyl, sulpho, ionizable sulphonarnide, and hydroxyl.

4. A process according to claim 3, wherein said colour coupler is present in the said emulsion layer.

5. A process of producing photographic colour images which comprises treating a developable silver halide emulsion layer in the presence of a colour coupler with a colour developing composition comprising an aromatic primary amino colour developing agent and then treating the developed emulsion layer with an alkaline composition comprising a tetraalkyl-pphenylene diamine compound corresponding to the formula:

wherein:

each of R,, R and R-, stands for C -C alkyl or R, together with R represents the atoms necessary to close a pyrrolidine ring, and R stands for C -C alkyl or ethylene or propylene linked to the C-atom of the phenylene ring in ortho position to the amino group thereof. 

2. A photographic developer composition according to claim 1, wherein the aromatic primary amino colour developing agent is a N,N-dialkyl-p-phenylene diamine or toluene analog thereof.
 3. A process of producing photographic colour images which comprises treating a developable silver halide emulsion layer in the presence of a colour coupler with a developer composition which comprises an aromatic primary amino colour developing agent and a tetraalkyl p-phenylene diamine compound corresponding to the general formula:
 4. A process according to claim 3, wherein said colour coupler is present in the said emulsion layer.
 5. A process of producing photographic colour images which comprises treating a developable silver halide emulsion layer in the presence of a colour coupler with a colour developing composition comprising an aromatic primary amino colour developing agent and then treating the developed emulsion layer with an alkaline composition comprising a tetraalkyl-p-phenylene diamine compound corresponding to the formula:
 6. A process according to claim 5, wherein the aromatic primary amino colour developing agent is a N-N-dialkyl-p-phenylene diamine or toluene analog thereof. 